WO2019215945A1 - 光学フィルタ及び光学フィルタの製造方法 - Google Patents

光学フィルタ及び光学フィルタの製造方法 Download PDF

Info

Publication number
WO2019215945A1
WO2019215945A1 PCT/JP2018/041869 JP2018041869W WO2019215945A1 WO 2019215945 A1 WO2019215945 A1 WO 2019215945A1 JP 2018041869 W JP2018041869 W JP 2018041869W WO 2019215945 A1 WO2019215945 A1 WO 2019215945A1
Authority
WO
WIPO (PCT)
Prior art keywords
light
optical filter
wavelength
absorption layer
substrate
Prior art date
Application number
PCT/JP2018/041869
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
雄一郎 久保
新毛　勝秀
Original Assignee
日本板硝子株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日本板硝子株式会社 filed Critical 日本板硝子株式会社
Publication of WO2019215945A1 publication Critical patent/WO2019215945A1/ja

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/023—Optical properties
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/26—Reflecting filters

Definitions

  • the present invention relates to an optical filter and a method for manufacturing the optical filter.
  • an imaging device using an image sensor such as a CCD (Charge Coupled Device) or CMOS (Complementary Metal Oxide Semiconductor)
  • various optical filters are arranged on the front surface of the image sensor to obtain an image having good color reproducibility.
  • an image sensor has spectral sensitivity in a wide wavelength range from an ultraviolet region to an infrared region.
  • human visibility exists only in the visible light region.
  • a technique is known in which an optical filter that shields infrared light is disposed on the front surface of an image pickup device in order to bring the spectral sensitivity of the image pickup device in the image pickup apparatus closer to human visibility.
  • Patent Document 1 describes a near-infrared cut filter having a norbornene-based resin substrate and a near-infrared reflective film.
  • the near-infrared reflective film is a dielectric multilayer film.
  • the norbornene-based resin substrate contains a near infrared absorber.
  • Patent Document 2 describes a near-infrared cut filter that includes a laminated plate having a resin layer on at least one surface of a glass substrate and satisfies a predetermined condition regarding transmittance.
  • the resin layer contains a near infrared absorber.
  • the near-infrared cut filter preferably has a dielectric multilayer film on at least one side of the laminate.
  • Patent Document 3 describes a near-infrared cut filter formed from a near-infrared absorber and a resin.
  • a near-infrared absorber is obtained from a predetermined phosphonic acid compound, a predetermined phosphoric acid ester compound, and a copper salt.
  • the given phosphonic acid compound has a monovalent group R 1 represented by —CH 2 CH 2 —R 11 bonded to the phosphorus atom P.
  • R 11 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a fluorinated alkyl group having 1 to 20 carbon atoms.
  • the dielectric multilayer film has a characteristic of changing the transmittance spectrum of the optical filter with respect to light incident at different incident angles, and in particular shifts the transmittance spectrum of the optical filter to the short wavelength side as the incident angle increases. For this reason, when the near-infrared cut filter described in Patent Document 1 is used together with the image pickup device of the image pickup apparatus, the image obtained by the image pickup apparatus has a central portion of the image because the angle of the light ray incident on the optical filter is different. And the peripheral portion of the image may have different colors.
  • “transmittance spectrum” refers to the transmittance (unit:%) of light incident on an optical filter or a part of a substrate constituting the optical filter and a functional film (functional layer) or a combination thereof. It means the one arranged in order of wavelength.
  • the near-infrared cut filter described in Patent Document 2 has a dielectric multilayer film
  • the resin layer contains a near-infrared absorber. Thereby, the incident angle dependence of the transmittance spectrum is reduced.
  • Patent Document 2 it is unclear how the dielectric multilayer film and the resin layer affect the transmittance spectrum of the near-infrared cut filter, and the incident angle dependence of the absorption wavelength is unknown. There is room for improvement.
  • the near-infrared cut filter described in Patent Document 3 does not require a dielectric multilayer film, and it is considered that the transmittance spectrum hardly shifts to the short wavelength side as the incident angle of light increases.
  • This infrared cut filter is advantageous from the viewpoint of absorbing and cutting infrared rays in a relatively wide wavelength range.
  • the infrared cut filter transmits infrared light of a predetermined wavelength or ultraviolet light of a predetermined wavelength, and optical characteristics exhibited by the infrared cut filter. May deviate from human visibility.
  • the transmission region means a wavelength range corresponding to a transmittance of 70% or more in the transmittance spectrum.
  • the present invention has an advantageous characteristic for bringing the spectral sensitivity of an image sensor close to human visual sensitivity, and has an optical characteristic having a desired characteristic without requiring a complicated process with a simple configuration.
  • the manufacturing method of such an optical filter is provided.
  • the present invention It contains a light absorber formed by phosphonic acid represented by the following formula (a) and copper ions, a phosphoric ester that disperses the light absorber, and a curable resin, and the light absorber is dispersed.
  • a light-absorbing layer formed by a cured product of the light-absorbing composition (I) having an average spectral transmittance of 80% or more at a wavelength of 450 nm to 600 nm, (II) has a spectral transmittance of 1% or less at a wavelength of 750 nm to 900 nm, (III) having an average spectral transmittance of 4% or less in the wavelength range of 350 nm to 370 nm; (IV) When a wavelength having a spectral transmittance that decreases with an increase in wavelength at a wavelength of 600 nm to 800 nm and a spectral transmittance of the optical filter at a wavelength of 600 nm to 800 nm is 50% is defined as
  • the infrared cutoff wavelength for light incident on the optical filter at an incident angle of 0 ° is 620 nm to 680 nm
  • (V) When the wavelength at which the spectral transmittance increases as the wavelength increases from 350 nm to 450 nm and the spectral transmittance of the optical filter is 50% at the wavelength of 350 nm to 450 nm is defined as the ultraviolet cutoff wavelength
  • the ultraviolet cut-off wavelength for light incident on the optical filter at an incident angle of 0 ° is 380 nm to 420 nm.
  • An optical filter is provided. [Wherein, R 11 represents a phenyl group or a halogenated phenyl group in which at least one hydrogen atom in the phenyl group is substituted with a halogen atom. ]
  • the present invention also provides: Providing a substrate having a surface containing an organic fluorine compound and having a surface roughness Ra specified by JIS B 0601: 1994 of 50 nm or less; It contains a light absorber formed by phosphonic acid represented by the following formula (a) and copper ions, a phosphoric ester that disperses the light absorber, and a curable resin, and the light absorber is dispersed. Applying a light absorbing composition on the surface of the substrate to form a coating film, curing the coating film to form a light absorption layer; Peeling the light absorption layer from the substrate, An optical filter manufacturing method is provided. [Wherein, R 11 represents a phenyl group or a halogenated phenyl group in which at least one hydrogen atom in the phenyl group is substituted with a halogen atom. ]
  • the optical filter described above has advantageous characteristics for bringing the spectral sensitivity of the image sensor close to human visual sensitivity, and has desired characteristics without requiring a complicated process with a simple configuration. Further, according to the above manufacturing method, an optical filter having a simpler configuration can be obtained.
  • FIG. 1 is a cross-sectional view showing an optical filter according to an example of the present invention.
  • FIG. 2 is a cross-sectional view showing an optical filter according to another example of the present invention.
  • FIG. 3 is a cross-sectional view showing an optical filter according to still another example of the present invention.
  • FIG. 4 is a cross-sectional view showing an optical filter according to still another example of the present invention.
  • FIG. 5 is a cross-sectional view showing an optical filter according to still another example of the present invention.
  • FIG. 6 is a cross-sectional view illustrating an imaging optical system including an optical filter according to an example of the present invention.
  • FIG. 7A is a transmittance spectrum of the optical filter according to the first embodiment.
  • 7B is another transmittance spectrum of the optical filter according to Example 1.
  • FIG. 7A is a transmittance spectrum of the optical filter according to the first embodiment.
  • 7B is another transmittance spectrum of the optical filter according to Example 1.
  • FIG. 7A is a
  • FIG. 8 is a transmittance spectrum of the optical filter according to Example 19.
  • FIG. 9 is a transmittance spectrum of the optical filter according to Example 20.
  • FIG. 10 is a transmittance spectrum of the optical filter according to Example 21.
  • FIG. 11 is a transmittance spectrum of the optical filter according to Example 22.
  • FIG. 12 is a transmittance spectrum of the optical filter according to Example 23.
  • FIG. 13 is a transmittance spectrum of the optical filter according to Example 24.
  • FIG. 14 is a transmittance spectrum of the optical filter according to Example 25.
  • FIG. 15 is a transmittance spectrum of the optical filter according to Comparative Example 4.
  • FIG. 16 is a transmittance spectrum of the optical filter according to Comparative Example 5.
  • FIG. 17 is a transmittance spectrum of the optical filter according to Comparative Example 6.
  • FIG. 18 is a transmittance spectrum of the optical filter according to Comparative Example 7.
  • optical filters 1 a to 1 e that are examples of the optical filter according to the present invention include a light absorption layer 10.
  • the light absorption layer 10 may be in a state of being disposed on a predetermined substrate, or may be in a state of being peeled off from the substrate after being formed on the predetermined substrate.
  • the light absorption layer 10 contains a light absorber formed by a phosphonic acid represented by the following formula (a) and copper ions, a phosphate ester in which the light absorber is dispersed, and a curable resin. It is formed with the hardened
  • the optical filters 1a to 1e satisfy the following (I) to (V).
  • the optical filters 1a to 1e have an average spectral transmittance of 80% or more at wavelengths of 450 nm to 600 nm.
  • the optical filters 1a to 1e have a spectral transmittance of 1% or less at wavelengths of 750 nm to 900 nm.
  • the optical filters 1a to 1e have an average spectral transmittance of 4% or less in the wavelength range of 350 nm to 370 nm.
  • the optical filters 1a to 1e have spectral transmittances that decrease as the wavelength increases at wavelengths of 600 nm to 800 nm.
  • the infrared cut-off wavelength When the wavelength at which the spectral transmittance of the optical filters 1a to 1e is 50% at wavelengths of 600 nm to 800 nm is defined as the infrared cut-off wavelength, the infrared side with respect to light incident on the optical filters 1a to 1e at an incident angle of 0 °
  • the cutoff wavelength is 620 nm to 680 nm.
  • the optical filters 1a to 1e have a spectral transmittance that increases as the wavelength increases at wavelengths of 350 nm to 450 nm.
  • the ultraviolet cutoff wavelength When the wavelength at which the spectral transmittance of the optical filters 1a to 1e is 50% at a wavelength of 350 to 450 nm is defined as the ultraviolet cutoff wavelength, the ultraviolet side with respect to light incident on the optical filters 1a to 1e at an incident angle of 0 °
  • the cutoff wavelength is 380 nm to 420 nm.
  • R 11 represents a phenyl group or a halogenated phenyl group in which at least one hydrogen atom in the phenyl group is substituted with a halogen atom.
  • the optical filters 1a to 1e satisfy the above condition (I)
  • the optical filters 1a to 1e satisfy the above condition (II)
  • the optical filters 1a to 1e can advantageously shield infrared rays of 750 nm to 900 nm.
  • the optical filters 1a to 1e can advantageously shield ultraviolet rays of 370 nm or less.
  • the spectral sensitivity of the image sensor can be advantageously brought close to human visual sensitivity.
  • the optical filters 1a to 1e satisfy the above conditions (IV) and (V), light in the infrared region and the ultraviolet region is advantageously shielded.
  • the spectral sensitivity of the image sensor can be advantageously brought close to human visual sensitivity.
  • the optical filters 1a to 1e desirably have an average spectral transmittance of 85% or more at wavelengths of 450 nm to 600 nm.
  • the optical filters 1a to 1e are arranged in front of the image sensor, the amount of visible light received by the image sensor is larger in the wavelength range of 450 nm to 600 nm.
  • the optical filters 1a to 1e desirably have a spectral transmittance of 0.5% or less at wavelengths of 750 nm to 900 nm.
  • the optical filters 1a to 1e desirably have an average spectral transmittance of 1% or less in a wavelength range of 350 nm to 370 nm.
  • the infrared cutoff wavelength for light incident on the optical filters 1a to 1e at an incident angle of 0 ° is preferably 630 nm or more or 660 nm or less.
  • the ultraviolet cutoff wavelength for light incident on the optical filters 1a to 1e at an incident angle of 0 ° is 390 nm or more, or 410 nm or less.
  • the optical filters 1a to 1e desirably satisfy the following (VI) and (VII).
  • (VI) The difference between the infrared cutoff wavelength for light incident on the optical filters 1a to 1e at an incident angle of 0 ° and the infrared cutoff wavelength for light incident on the optical filters 1a to 1e at an incident angle of 40 ° is It is 20 nm or less, desirably 10 nm or less.
  • the difference between the ultraviolet cutoff wavelength for light incident on the optical filters 1a to 1e at an incident angle of 0 ° and the ultraviolet cutoff wavelength for light incident on the optical filters 1a to 1e at an incident angle of 40 ° is It is 20 nm or less, desirably 10 nm or less.
  • the spectral sensitivity of the image sensor is incident on the image sensor when the optical filters 1a to 1e are arranged in front of the image sensor. Difficult to change depending on the incident angle of light.
  • the optical filter 1a to the optical filter 1d further include a transparent dielectric substrate 20, for example.
  • the transparent dielectric substrate 20 in the optical filters 1a to 1d is, for example, a dielectric substrate having an average spectral transmittance of 90% or more at 450 nm to 600 nm.
  • the transparent dielectric substrate 20 may be a substrate made of glass containing CuO (copper oxide) having absorption ability in the infrared region. Even in this case, the optical filters 1a to 1d satisfying the above conditions (I) to (V) can be obtained.
  • the transparent dielectric substrate 20 may have an average spectral transmittance of 90% or more at a wavelength of 350 nm to 900 nm, for example.
  • the material of the transparent dielectric substrate 20 is not limited to a specific material, but is, for example, predetermined glass or resin.
  • the transparent dielectric substrate 20 is, for example, transparent glass or infrared cut glass made of silicate glass such as soda lime glass and borosilicate glass.
  • the infrared cut glass is, for example, phosphate glass or fluorophosphate glass containing CuO.
  • the transparent dielectric substrate 20 is an infrared cut glass, the infrared absorption ability required for the light absorption layer 10 can be reduced by the infrared absorption ability of the infrared cut glass. As a result, the thickness of the light absorption layer 10 can be reduced, or the concentration of the light absorber contained in the light absorption layer 10 can be reduced.
  • the infrared cut-off wavelength in the transmittance spectrum of the infrared cut glass tends to exist on the relatively long wavelength side. For this reason, the light-absorbing composition is cured to form the light-absorbing layer 10 on the transparent dielectric substrate 20 that is an infrared-cut glass, so that the infrared-side cutoff wavelengths of the optical filters 1a to 1d are shorter. And the spectral sensitivity of the image sensor is easily matched to human visual sensitivity.
  • the resin may be, for example, a cyclic olefin resin such as a norbornene resin, a polyarylate resin, an acrylic resin, a modified acrylic resin, a polyimide resin, a polyetherimide resin, or a polysulfone. Resin, polyethersulfone resin, polycarbonate resin, or silicone resin.
  • the optical filter 1e does not include a substrate such as a transparent dielectric substrate.
  • the optical filter 1e is a substrate-less optical filter.
  • the thickness of the optical filter 1e tends to be small.
  • the phosphonic acid forming the light absorber includes a phenyl group or a halogenated phenyl group in which at least one hydrogen atom in the phenyl group is substituted with a halogen atom. Since the phenyl group and the halogenated phenyl group have high lipophilicity, they have high compatibility with an organic solvent such as toluene, and the light absorber hardly aggregates.
  • the light absorption layer 10 of the optical filters 1a to 1e tends to have a flexible structure due to the phenyl group or the halogenated phenyl group of the phosphonic acid forming the light absorber. As a result, the light absorption layer 10 has good crack resistance.
  • the ratio of the phosphonic acid content to the phosphoric acid ester content in the light-absorbing composition containing the light-absorbing agent formed by the phosphonic acid represented by the formula (a) and copper ions is, for example, on a mass basis.
  • the ratio of the phosphonic acid content to the copper ion content is, for example, 0.45 to 0.80 on the basis of the substance amount (mole).
  • the ratio of the content of phosphonic acid to the content of phosphate ester is 0.10 to 0.48 on a mass basis, and the content of copper ions
  • the ratio of the content of phosphonic acid to the amount is 0.45 to 0.80 on the basis of the amount of substance.
  • the light-absorbing composition may further contain an auxiliary light absorber formed of phosphonic acid represented by the following formula (b) and copper ions.
  • auxiliary light absorber formed of phosphonic acid represented by the following formula (b) and copper ions.
  • the light absorption layer 10 of the optical filters 1a to 1e further contains an auxiliary light absorber formed of phosphonic acid and copper ions represented by the above formula (b).
  • the transmittance of light having a wavelength of 850 nm or more or a wavelength of 900 nm or more of the optical filters 1a to 1e can be advantageously reduced.
  • the alkyl group as R 12 may be either a straight chain or a branched chain.
  • the ratio of the content of the phosphonic acid represented by the formula (b) to the content of the phosphonic acid represented by the formula (a) is, for example, from 0.05 to 0.50 on a mass basis, and desirably is a ratio of 0.00. 07 to 0.30.
  • the phosphate ester contained in the light-absorbing composition is not particularly limited as long as the light absorber can be appropriately dispersed.
  • the phosphate ester represented by the following formula (c1) and the formula (c2) At least one of phosphoric acid monoesters. Thereby, it can disperse
  • R 21 , R 22 , and R 3 are each a monovalent functional group represented by — (CH 2 CH 2 O) n R 4 . , N is an integer of 1 to 25, and R 4 represents an alkyl group having 6 to 25 carbon atoms.
  • R 21 , R 22 , and R 3 are the same or different types of functional groups.
  • the light absorber is formed, for example, by coordination of a phosphonic acid represented by the formula (a) to a copper ion.
  • fine particles containing at least a light absorber are formed in the light absorbing composition.
  • the fine particles are dispersed in the light-absorbing composition without aggregating due to the action of the phosphate ester.
  • the average particle diameter of the fine particles is, for example, 5 nm to 200 nm. If the average particle diameter of the fine particles is 5 nm or more, a special process is not required for finer fine particles, and there is little possibility that the structure of the fine particles containing at least the light absorber is broken. Further, fine particles are well dispersed in the light absorbing composition.
  • the average particle diameter of the fine particles is desirably 100 nm or less.
  • the average particle diameter of the fine particles is more desirably 75 nm or less. In this case, the transparency of the light absorption layer with respect to visible light is particularly high.
  • the average particle diameter of the fine particles can be measured by a dynamic light scattering method.
  • the auxiliary light absorber is formed, for example, by coordination of phosphonic acid represented by the formula (b) to copper ions. Further, for example, fine particles containing at least an auxiliary light absorber are formed in the light absorbing composition.
  • the average particle size of the fine particles containing the auxiliary light absorber is, for example, the same as the average particle size of the fine particles containing the light absorber.
  • the source of copper ions in the light absorbing composition is, for example, a copper salt.
  • the copper salt is, for example, copper acetate or copper hydrate.
  • copper salts include copper chloride, copper formate, copper stearate, copper benzoate, copper pyrophosphate, copper naphthenate, and copper citrate anhydrides or hydrates.
  • copper acetate monohydrate is expressed as Cu (CH 3 COO) 2 .H 2 O, and 1 mol of copper ion is supplied by 1 mol of copper acetate monohydrate.
  • the curable resin of the light-absorbing composition is, for example, a resin in which a light absorbent can be dispersed, heat-curing or ultraviolet-curing is possible, and the cured product is transparent to light having a wavelength of 350 nm to 900 nm. It is.
  • the content of the phosphonic acid represented by the formula (a) is, for example, 3 to 180 parts by mass with respect to 100 parts by mass of the curable resin.
  • the curable resin of the light absorbing composition is desirably polysiloxane (silicone resin).
  • the polysiloxane desirably contains an aryl group such as a phenyl group. If the resin layer included in the optical filter is hard (rigid), cracks are likely to occur due to curing shrinkage during the manufacturing process of the optical filter as the thickness of the resin layer increases.
  • the curable resin of the light-absorbing composition is an aryl group-containing polysiloxane, the light-absorbing layer formed by the light-absorbing composition tends to have good crack resistance.
  • the polysiloxane containing an aryl group has high compatibility with a phosphonic acid having a phenyl group or a halogenated phenyl group, and the light absorber is less likely to aggregate.
  • the curable resin of the light absorbing composition is a polysiloxane containing an aryl group
  • the phosphoric acid ester contained in the light absorbing composition is represented by the formula (c1) or the formula (c2). It is desirable to have a linear organic functional group having flexibility such as an oxyalkyl group such as an ester.
  • a light absorber This is because a light-absorbing layer having both high rigidity and good flexibility can be formed by curing the light-absorbing composition with high compatibility with the curable resin and the phosphate ester.
  • Specific examples of polysiloxanes that can be used as curable resins include KR-255, KR-300, KR-2621-1, KR-211, KR-311, KR-216, KR-212, and KR-251.
  • silicone resins manufactured by Shin-Etsu Chemical Co., Ltd.
  • resins such as an acrylic resin, an epoxy resin, and a vinyl acetal resin can also be used.
  • these resin may contain any of a monofunctional or polyfunctional monomer, oligomer, and polymer as a structural unit.
  • Polysiloxane silicon resin
  • SiO 2 glass substrate containing SiO 2 or a dielectric film whose layer in contact with polysiloxane is an SiO 2 layer.
  • a copper salt such as copper acetate monohydrate is added to a predetermined solvent such as tetrahydrofuran (THF) and stirred to obtain a copper salt solution.
  • a phosphoric acid ester compound such as a phosphoric acid diester represented by the formula (c1) and a phosphoric acid monoester represented by the formula (c2) is added to the solution of the copper salt and stirred to prepare a solution A.
  • the phosphonic acid represented by the formula (a) is added to a predetermined solvent such as THF and stirred to prepare a liquid B.
  • the phosphonic acid represented by the formula (b) may be added to a predetermined solvent as necessary.
  • the liquid B is added to the liquid A and stirred for a predetermined time.
  • a predetermined solvent such as toluene is added to this solution and stirred to obtain liquid C.
  • the solvent removal treatment is performed for a predetermined time while heating the C solution.
  • components generated by dissociation of a solvent such as THF and a copper salt such as acetic acid (boiling point: about 118 ° C.) are removed, and a light absorber is generated by the phosphonic acid represented by the formula (a) and copper ions. Is done.
  • the temperature at which the liquid C is heated is determined based on the boiling point of the component to be removed that has dissociated from the copper salt.
  • a solvent such as toluene (boiling point: about 110 ° C.) used for obtaining the liquid C is also volatilized. Since it is desirable for this solvent to remain to some extent in the light-absorbing composition, the addition amount of the solvent and the time for desolvation treatment are preferably determined from this viewpoint.
  • it in order to obtain C liquid, it can replace with toluene and can use o-xylene (boiling point: about 144 degreeC). In this case, since the boiling point of o-xylene is higher than that of toluene, the addition amount can be reduced to about one-fourth of the addition amount of toluene.
  • a curable resin such as polysiloxane (silicone resin) is added and stirred for a predetermined time.
  • the light absorbing composition according to the present invention can be prepared in this manner.
  • the solvent used for the preparation of the light-absorbing composition desirably has a predetermined polarity from the viewpoint of appropriately forming a light absorber with the phosphonic acid represented by formula (a) and copper ions. This is because the polarity of the solvent affects the dispersion in the light-absorbing composition of the fine particles containing at least the light-absorbing agent.
  • a solvent having an appropriate polarity is selected according to the type of phosphate ester used for preparing the liquid A.
  • the light absorption layer 10 in the optical filters 1a to 1e has a thickness of 30 ⁇ m to 800 ⁇ m, for example. Accordingly, the optical filters 1a to 1e advantageously satisfy the conditions (I) to (V). As shown in FIG. 3, when the light absorption layer 10 is divided into two or more layers, the total thickness of each layer is determined as the thickness of the light absorption layer 10. As described above, when a polysiloxane containing an aryl group is used as a curable resin for a light-absorbing composition, a light-absorbing layer having both good rigidity and good flexibility can be formed by curing the light-absorbing composition. .
  • the thickness of the light-absorbing layer 10 can be relatively easily increased, and a large amount of light-absorbing agent can be included in the light-absorbing layer. it can.
  • the thickness of the light-absorbing layer 10 in the optical filters 1a to 1e is desirably 80 ⁇ m to 500 ⁇ m, more desirably 100 ⁇ m to 400 ⁇ m. is there.
  • a liquid light-absorbing composition is applied to one main surface of the transparent dielectric substrate 20 by spin coating or dispenser coating to form a coating film.
  • the coating film is cured by performing a predetermined heat treatment on the coating film.
  • the optical filter 1a can be manufactured.
  • the maximum value of the atmospheric temperature of the coating film in the heat treatment is, for example, 140 ° C. or higher, and preferably 160 ° C. or higher.
  • the maximum value of the atmospheric temperature of the coating film in heat processing is 170 degrees C or less, for example.
  • the optical filter 1 b includes an infrared reflective film 30.
  • the infrared reflective film 30 is a film formed by laminating a plurality of materials having different refractive indexes.
  • the material for forming the infrared reflective film 30 is, for example, an inorganic material such as SiO 2 , TiO 2 , and MgF 2 or an organic material such as a fluororesin.
  • the laminated body in which the infrared reflective film 30 is formed on the transparent dielectric substrate for example, transmits light having a wavelength of 350 nm to 800 nm and reflects light having a wavelength of 850 nm to 1200 nm.
  • the laminate including the infrared reflecting film 30 has a spectral transmittance of, for example, 85% or more, desirably 90% or more at a wavelength of 350 nm to 800 nm, and desirably, for example, 1% or less at a wavelength of 850 nm to 1200 nm.
  • the optical filter 1b can more effectively shield light in the wavelength range of 850 nm to 1200 nm or light in the wavelength range of 900 nm to 1200 nm.
  • the spectral transmittance of the laminate including the infrared reflecting film 30 has the above-described characteristics, the shift of the transmittance spectrum of the stacked body including the infrared reflecting film 30 due to a change in the incident angle of light causes the optical filter 1b. The influence on the transmittance spectrum can be suppressed. This is because the light absorbing agent formed by the phosphonic acid represented by the formula (a) and the copper ion is in the region where the wavelength shift appears in the transmission spectrum of the infrared reflecting film with the fluctuation of the incident angle of light. It is for having.
  • the method for forming the infrared reflective film 30 of the optical filter 1b is not particularly limited, and vacuum deposition, sputtering, CVD (Chemical Vapor Deposition), and spin coating or spraying are performed depending on the type of material forming the infrared reflective film 30. Any of the sol-gel methods using a coating can be used.
  • the light absorption layer 10 is formed on both main surfaces of the transparent dielectric substrate 20.
  • the thickness of the light absorption layer required for the optical filter 1c to obtain desired optical characteristics can be ensured by the two light absorption layers 10 instead of the one light absorption layer 10.
  • the thickness of the light absorption layer 10 on both main surfaces of the transparent dielectric substrate 20 may be the same or different. That is, the light absorption layer 10 is formed on both main surfaces of the transparent dielectric substrate 20 so that the thickness of the light absorption layer necessary for the optical filter 1c to obtain desired optical characteristics is evenly or unevenly distributed. Is formed.
  • each light absorption layer 10 formed on both main surfaces of the transparent dielectric substrate 20 is relatively small. For this reason, the dispersion
  • the transparent dielectric substrate 20 is very thin, if the light absorbing layer 10 is formed only on one main surface of the transparent dielectric substrate 20, the shrinkage that occurs when the light absorbing layer 10 is formed from the light absorbing composition. The associated stress can cause the optical filter to warp. However, since the light absorption layer 10 is formed on both main surfaces of the transparent dielectric substrate 20, even when the transparent dielectric substrate 20 is very thin, warpage is suppressed in the optical filter 1c.
  • the optical filter 1 d further includes an auxiliary light absorbing layer 15 formed in parallel with one main surface of the transparent dielectric substrate 20.
  • the auxiliary light absorbing layer 15 includes, for example, an auxiliary light absorber formed of the phosphonic acid represented by the above formula (b) and copper ions, a phosphate ester in which the auxiliary light absorber is dispersed, and curable properties. It is formed with the hardened
  • the light absorption layer 10 is formed on one main surface of the transparent dielectric substrate 20, and the auxiliary light absorption layer 15 is formed on the other main surface of the transparent dielectric substrate 20.
  • the stress applied to the transparent dielectric substrate 20 with the formation of the light absorption layer 10 and the stress applied to the transparent dielectric substrate 20 with the formation of the auxiliary light absorption layer 15 are balanced, and the optical filter 1d is warped. Can be prevented.
  • the same materials as the phosphate ester and the curable resin in the light absorbing composition can be used.
  • the liquid auxiliary light-absorbing composition is applied to one main surface of the transparent dielectric substrate 20 by spin coating or dispenser coating to form a coating film.
  • the coating film is cured by performing a predetermined heat treatment on the coating film.
  • the optical filter 1d can be manufactured.
  • the maximum value of the atmospheric temperature of the coating film in the heat treatment is, for example, 140 ° C. or higher, and preferably 160 ° C. or higher.
  • the maximum value of the atmospheric temperature of the coating film in heat processing is 170 degrees C or less, for example.
  • the heat treatment for forming the light absorption layer 10 and the auxiliary light absorption layer 15 may be performed simultaneously.
  • the optical filter 1e according to another example of the present invention is substrate-less.
  • An example of the manufacturing method of the optical filter 1e will be described.
  • a liquid light-absorbing composition is applied to one main surface of a predetermined substrate by spin coating or dispenser application to form a coating film.
  • this coating film is subjected to a predetermined heat treatment to cure the coating film to obtain a light absorbing layer.
  • the optical absorption layer can be manufactured by peeling the light absorption layer from the substrate.
  • the surface roughness Ra defined in the Japanese Industrial Standard (JIS) B 0601: 1994 in the substrate is, for example, 50 nm or less, desirably 10 nm or less, and more desirably 5 nm or less.
  • the material and transparency of the substrate are not particularly limited.
  • a substrate a glass substrate, a metal substrate, a ceramic substrate, and a resin substrate can be used.
  • the use of a glass substrate is desirable because it has a smooth surface, substrates with various thicknesses can be easily obtained, and is inexpensive.
  • a glass substrate with a release film is used.
  • a glass substrate having a film (surface) containing an organic fluorine compound is provided. Then, the light absorbing composition is applied onto the surface of the substrate to form a coating film, and the coating film is cured to form a light absorption layer.
  • the film (surface) containing the organic fluorine compound can be peeled from the glass substrate without damaging the light absorption layer.
  • the surface roughness of the surface of the glass substrate on which a release film such as a film containing such an organic fluorine compound is formed is preferably maintained within the above range.
  • the substrate is not particularly limited, but a fluororesin substrate such as polytetrafluoroethylene, polychlorotrifluoroethylene, and polyvinyl fluoride can also be used.
  • the substrate desirably has a surface that includes an organofluorine compound.
  • a substrate in which a film containing an organic fluorine compound is formed on a glass substrate having a smooth surface for releasing the light absorbing layer is not limited to a specific compound as long as desired release properties can be imparted to the substrate.
  • the organic fluorine compound includes, for example, perfluoropolyether.
  • a glass substrate with a release film can be produced by applying a coating liquid containing OPTOOL DSX manufactured by Daikin Industries, Ltd. to one main surface of a glass substrate.
  • the coating liquid can be applied by coating such as spin coating, dip coating, and spray coating.
  • the coating liquid is applied to one main surface of the glass substrate to form a coating film, and after the coating film is sufficiently dried, it is converted to a liquid containing an inert organic fluorine compound such as hydrofluoroether. It is effective to immerse the glass substrate and perform ultrasonic treatment. This is because the excess organic fluorine compound is removed.
  • a part of the film containing the organic fluorine compound May enter the light absorbing layer.
  • some components of the film containing the organic fluorine compound may be transferred onto the light absorption layer.
  • an organic fluorine compound can be included in the light absorption layer.
  • the light absorption layer can contain 10 mass% or less of fluorine atoms.
  • the fluorine atom contained in the light absorption layer is desirably 5% by mass or less, and more desirably 1% by mass or less.
  • a frame is disposed on the surface of a substrate such as a substrate having a surface containing an organic fluorine compound, and the light absorbing composition is applied on the inside of the frame and on the surface of the substrate.
  • the frame is preferably formed of a material having an Asker C hardness of 10 to 80.
  • the light absorption layer desirably has a thickness of 30 ⁇ m or more.
  • the viscosity of the light-absorbing composition is low, the light-absorbing composition flows out of the desired range on the glass substrate and has a sufficient thickness. It is difficult to obtain a layer. Therefore, if a frame that functions as a dam for preventing the light-absorbing composition from flowing out is used, a light-absorbing layer having an appropriate thickness can be easily obtained.
  • the shape of the frame is not particularly limited, but may be, for example, a quadrangular shape in a plan view, and may be a mouth shape.
  • the frame desirably adheres to the glass substrate to such an extent that the light-absorbing composition does not leak from the gap, and can be separated from the glass substrate after the light-absorbing layer is formed.
  • the material of the frame is, for example, resin, glass, or metal.
  • the material of the frame is desirably a resin, and more desirably a resin such as polyurethane and silicone. These resins are moderately soft and have an appropriate adhesion to the smooth surface of the glass substrate, and a resin frame can be disposed on the glass substrate without any special surface treatment.
  • the resin hardness of the resin frame is, for example, 10 to 80 in Asker C hardness, and preferably 10 to 65 in Asker C hardness.
  • the resin has such hardness, it is possible to easily attach the resin frame to the glass and to easily peel the resin frame from the glass.
  • the thickness of the light absorption layer has a specific thickness of, for example, 30 ⁇ m or more, the light absorption layer can be peeled off from the glass substrate together by peeling the frame from the glass substrate, making the optical filter easy. Can be manufactured.
  • the frame is made of resin, the light-absorbing composition also contains resin, so the adhesion to the resin frame is likely to be high, and a certain degree of unity occurs, which is realized. It becomes possible.
  • the hardness of the frame material can be evaluated in accordance with JIS K7312: 1996.
  • the push needle is pushed in to obtain the hardness value from the pushing depth Can do.
  • the measurement value for example, five points are measured at points separated by 6 mm or more, and the median value is adopted.
  • a predetermined heat treatment is performed to cure the coating film of the light absorbing composition.
  • the conditions for the heat treatment are, for example, the same as the heat treatment conditions in the production of the optical filter 1a.
  • the optical filter 1 e may be changed to an optical filter further including an antireflection film formed on one main surface of the light absorption layer 10 or both main surfaces of the light absorption layer 10.
  • the antireflection film is formed to form an interface between the optical filter and air, and is a film for reducing reflection of light in the visible light region.
  • the antireflection film is made of a dielectric material such as resin, oxide, and fluoride.
  • the antireflection film may be a multilayer film formed by laminating two or more kinds of dielectrics having different refractive indexes.
  • the antireflection film may be a dielectric multilayer film made of a low refractive index material such as SiO 2 and a high refractive index material such as TiO 2 or Ta 2 O 5 .
  • a resin layer containing a silane coupling agent may be formed between the light absorption layer and the antireflection film in order to improve the adhesion of the antireflection film.
  • the imaging optical system 100 can be provided using the optical filter 1a.
  • the imaging optical system 100 further includes, for example, an imaging lens 3 in addition to the optical filter 1a.
  • the imaging optical system 100 is disposed in front of the imaging element 2 in an imaging apparatus such as a digital camera.
  • the image sensor 2 is an image sensor such as a CCD or a CMOS, for example.
  • the light from the subject is collected by the imaging lens 3, and the ultraviolet and infrared rays are cut by the optical filter 1 a and then incident on the imaging device 2.
  • the spectral sensitivity of the image sensor 2 is close to human visual sensitivity, and a good image with high color reproducibility can be obtained.
  • the imaging optical system 100 may include any one of the optical filter 1b, the optical filter 1c, the optical filter 1d, and the optical filter 1e instead of the optical filter 1a.
  • the present invention will be described in more detail by way of examples.
  • the present invention is not limited to the following examples.
  • First, the evaluation method regarding the spectral transmittance of the optical filter according to the example and the comparative example will be described.
  • the transmittance spectrum when light having a wavelength in the range of 300 nm to 1200 nm is incident on the optical filters according to some examples and some comparative examples is measured with an ultraviolet-visible spectrophotometer (product name: V manufactured by JASCO Corporation). -670).
  • the incident angle of incident light to the optical filters according to some examples and some comparative examples was set to 0 ° (degrees).
  • the transmittance in the wavelength range of 750 nm to 900 nm was normalized so as to have a predetermined value.
  • the transmittance spectrum measured for optical filters according to some examples and some comparative examples is multiplied by 100/92 to cancel reflection at the interface, and the transmittance at each wavelength is converted to absorbance.
  • the normalized transmission spectrum was calculated by further multiplying the value adjusted by multiplying by the normalization coefficient by 92/100.
  • the normalization coefficient was determined according to each of the following two conditions (1) and (2).
  • the above conditions (1) and (2) for determining the normalization coefficient were determined with reference to transmittance characteristics in the wavelength range of 750 nm to 900 nm required for the optical filter.
  • a layer (light absorption layer) having an appropriate thickness for example, about 50 ⁇ m to 100 ⁇ m is formed using the material to be studied. It is efficient to normalize a transmittance spectrum actually measured for a laminate sample having a layer under a predetermined condition and then evaluate a subject to be examined based on a result of the normalization.
  • the thickness of the layer may be adjusted so as to obtain a desired transmittance spectrum in accordance with materials and conditions that have yielded positive results in such evaluation. .
  • a transmittance spectrum when light having a wavelength in the range of 300 nm to 1200 nm is incident on optical filters according to some examples and some comparative examples at incident angles of 0 ° and 40 ° is obtained by an ultraviolet-visible spectrophotometer ( It was measured using JASCO Corporation, product name: V-670) and normalized as described above.
  • the transmittance spectrum is compared with the normalized transmittance spectrum at an incident angle of 0 ° and the normalized transmittance spectrum at an incident angle of 40 °. The incidence angle dependence of was evaluated.
  • Example 1 1.125 g of copper acetate monohydrate and 60 g of tetrahydrofuran (THF) were mixed and stirred for 3 hours to obtain a copper acetate solution. Next, 1.55 g of Prisurf A208F (Daiichi Kogyo Seiyaku Co., Ltd.), which is a phosphate ester compound, was added to the obtained copper acetate solution and stirred for 30 minutes to obtain Liquid A. To 0.4277 g of phenylphosphonic acid (manufactured by Nissan Chemical Industries), 10 g of THF was added and stirred for 30 minutes to obtain a solution B-1.
  • Prisurf A208F Diichi Kogyo Seiyaku Co., Ltd.
  • the solution C was placed in a flask and heated with an oil bath (Tokyo Rika Kikai Co., Ltd., model: OSB-2100), and the solvent was removed by a rotary evaporator (Tokyo Rika Instruments Co., Ltd., model: N-1110SF) for 18 minutes. Processed. The set temperature of the oil bath was adjusted to 105 ° C. Thereafter, the solution after the solvent removal treatment was taken out of the flask. To the extracted solution, 4.400 g of a silicone resin (manufactured by Shin-Etsu Chemical Co., Ltd., product name: KR-300) was added and stirred at room temperature for 30 minutes to obtain a light-absorbing composition according to Example 1. Table 1 shows the amount of each material added. The light-absorbing composition according to Example 1 had high transparency, and in the light-absorbing composition according to Example 1, the light absorbent fine particles were well dispersed.
  • an oil bath Tokyo Rika Kikai Co., Ltd., model: OSB-2100
  • a dispenser in the range of about 30 mm ⁇ 30 mm at the center of one main surface of a transparent glass substrate (product name: D263, manufactured by SCHOTT) made of borosilicate glass having dimensions of 76 mm ⁇ 76 mm ⁇ 0.21 mm
  • a transparent glass substrate having an undried coating film is placed in an oven, and the conditions are 85 ° C. for 3 hours, then 125 ° C. for 3 hours, then 150 ° C. for 1 hour, and then 170 ° C. for 3 hours.
  • the coating film was heated to cure the coating film, and an optical filter according to Example 1 having a light absorption layer was produced.
  • FIGS. 7A and 7B show transmittance spectra of the optical filter according to Example 1 normalized according to the above conditions (1) and (2), respectively.
  • Table 2 shows main values in the normalized transmittance spectrum of the optical filter according to the first embodiment. As shown in FIGS. 7A and 7B and Table 2, it was confirmed that the above conditions (I) to (V) were satisfied in the optical filter according to Example 1 including the light absorption layer. Further, as a result of comparison between the normalized transmittance spectrum at the incident angle of 0 ° and the normalized transmittance spectrum at the incident angle of 40 ° with respect to the optical filter according to the example 1, the optical filter according to the example 1 Satisfied the above conditions (VI) and (VII). It was suggested that the optical filter according to Example 1 has desirable characteristics for use with an image sensor in an imaging apparatus.
  • Example 2 1.125 g of copper acetate monohydrate and 60 g of THF were mixed and stirred for 3 hours to obtain a copper acetate solution. Next, 2.3382 g of Prisurf A208F (Daiichi Kogyo Seiyaku Co., Ltd.), which is a phosphate ester compound, was added to the obtained copper acetate solution and stirred for 30 minutes to obtain Liquid A. Further, 10 g of THF was added to 0.5848 g of phenylphosphonic acid (manufactured by Nissan Chemical Industries, Ltd.), followed by stirring for 30 minutes to obtain a liquid B. Next, B liquid was added to A liquid, stirring A liquid, and it stirred at room temperature for 1 minute.
  • Prisurf A208F (Daiichi Kogyo Seiyaku Co., Ltd.)
  • Example An optical filter according to Example 2 was prepared in the same manner as in Example 1 except that the light absorbing composition according to Example 2 was used instead of the light absorbing composition according to Example 1.
  • Table 2 shows main values in the transmittance spectrum of the optical filter according to Example 2, normalized according to the above conditions (1) and (2). As shown in Table 2, it was confirmed that the above-mentioned conditions (I) to (V) were satisfied in the optical filter according to Example 2 provided with the light absorption layer. Further, as a result of comparison between the normalized transmittance spectrum at the incident angle of 0 ° and the normalized transmittance spectrum at the incident angle of 40 ° with respect to the optical filter according to the embodiment 2, the optical filter according to the embodiment 2 Satisfied the above conditions (VI) and (VII). It was suggested that the optical filter according to Example 2 has desirable characteristics for use with the image sensor in the imaging device.
  • Examples 3 to 18 The light absorbing compositions according to Examples 3 to 15 were obtained in the same manner as in Example 2, except that the addition amounts of phenylphosphonic acid and phosphate ester compound (Plysurf A208F) were changed as shown in Table 1.
  • Example 2 except that NIKKOL DDP-2 (manufactured by Nikko Chemicals Co., Ltd.) was used as the phosphate ester compound instead of Prisurf A208F, and the addition amounts of phenylphosphonic acid and phosphate ester compound were adjusted as shown in Table 1.
  • the light absorbing composition according to Example 16 was obtained.
  • Example 2 except that NIKKOL DDP-6 (manufactured by Nikko Chemicals Co., Ltd.) was used as the phosphate ester compound instead of Prisurf A208F, and the addition amounts of phenylphosphonic acid and phosphate ester compound were adjusted as shown in Table 1. Similarly, the light absorptive composition concerning Example 17 was obtained.
  • R 5 is a phosphate ester compound which is a monovalent group having 12 to 15 carbon atoms.
  • a light-absorbing composition according to Example 18 was obtained in the same manner as in Example 2 except that the addition amounts of the phenylphosphonic acid and the phosphate ester compound were adjusted as shown in Table 1. In the light-absorbing compositions according to Examples 3 to 18, the light absorbent fine particles were well dispersed.
  • Example 2 shows main values in the transmittance spectra of the optical filters according to Examples 3 to 18 normalized according to the above conditions (1) and (2). As shown in Table 2, it was confirmed that the above-mentioned conditions (I) to (V) were satisfied in the optical filters according to Examples 3 to 18 including the light absorption layer. Further, in each of the optical filters according to Examples 3 to 18, the results were compared from the result of comparison between the normalized transmittance spectrum at the incident angle of 0 ° and the normalized transmittance spectrum at the incident angle of 40 °. The optical filters according to Examples 3 to 18 satisfied the above conditions (VI) and (VII). It was suggested that the optical filters according to Examples 3 to 18 have desirable characteristics for use with the image sensor in the imaging device.
  • Examples 19 to 24> The light-absorbing composition according to Example 1 was applied to one main surface of a transparent glass substrate (manufactured by SCHOTT, product name: D263) made of borosilicate glass having dimensions of 76 mm ⁇ 76 mm ⁇ 0.21 mm.
  • a transparent glass substrate having an undried coating film is placed in an oven and coated at 85 ° C. for 3 hours, then at 125 ° C. for 3 hours, then at 150 ° C. for 1 hour, then at 170 ° C. for 8 hours.
  • a heat treatment was performed on the coating, the coating film was cured, and an optical filter according to Example 19 provided with a light absorption layer was obtained.
  • the thickness of the light absorption layer of the optical filter according to Example 19 was adjusted so that the maximum light transmittance at a wavelength of 750 nm to 900 nm was 0.4 to 0.5%.
  • the thickness of the light absorption layer of the optical filter according to Example 19 was determined based on the result of the transmittance spectrum of the optical filter according to Example 1 normalized under the condition (2).
  • the transmittance spectra of the optical filters according to Examples 19 to 24 are shown in FIGS. 8 to 13, respectively.
  • Table 3 shows main values concerning the transmittance of the optical filters according to Examples 19 to 24 and the thickness of the light absorption layer. The thickness of the light absorption layer was measured with a digital micrometer. It was confirmed that the optical filters according to Examples 19 to 24 satisfied the conditions (I) to (V). In addition, according to Examples 19 to 24, it was suggested that the optical filter normalized by the condition (2) can be reproduced. It was suggested that the optical filters according to Examples 19 to 24 have desirable characteristics for use with the image sensor in the imaging device.
  • Optool DSX (Daikin Kogyo Co., Ltd., active ingredient concentration: 20% by weight) 0.1 g and hydrofluoroether-containing solvent (3M Co., product name: Novec 7100) 19.9 g were mixed and stirred for 5 minutes.
  • a coating solution (active ingredient concentration: 0.1% by weight) was prepared.
  • This coating solution was applied to a transparent glass substrate (manufactured by SCHOTT, product name: D263 Teco) made of borosilicate glass having dimensions of 76 mm ⁇ 76 mm ⁇ 0.21 mm by spin coating at a rotation speed of 3000 rpm.
  • a coating film was formed. Thereafter, the coating film was allowed to stand at room temperature for 24 hours to obtain a glass with a release film.
  • a rectangular frame having an outer size of 70 mm ⁇ 70 mm, an inner size of 50 mm ⁇ 50 mm, a width of 10 mm, and a height of about 5 mm was disposed on the release film of the glass substrate with a release film.
  • the frame is made of a polyurethane resin (manufactured by Polysys, Asker C hardness: 15), and the glass substrate and the frame are made with care so that air does not enter between the glass substrate and the frame made of the polyurethane resin. Was brought into close contact.
  • the dispenser inside the frame the light absorbing composition prepared in the same manner as in Example 1 was applied to form a coating film.
  • the glass substrate having an undried coating film was placed in an oven and heat-treated at 85 ° C. for 3 hours. Thereafter, the glass substrate was taken out of the oven and the frame was peeled off from the glass substrate, whereby the optical filter semi-finished product and the frame formed inside the frame were peeled together from the substrate. Further, the semi-finished product of the optical filter is removed from the frame, and the semi-finished product of the optical filter is put in an oven and subjected to heat treatment at 125 ° C. for 3 hours, 150 ° C. for 1 hour, and 170 ° C. for 3 hours, Was completely cured. As a result, an optical filter according to Example 25 was obtained. The thickness of the optical filter according to Example 25 was 132 ⁇ m. The thickness of the optical filter according to Example 25 was measured with a digital micrometer.
  • FIG. 14 shows the transmittance spectrum of the optical filter according to Example 25.
  • Table 4 shows characteristics relating to the conditions (I) to (V) of the transmittance spectrum of the optical filter according to Example 25 read from the transmittance spectrum.
  • the optical filter according to Example 25 satisfied the above conditions (I) to (V), and it was suggested that the optical filter had desirable characteristics for use with the image sensor in the imaging device. Note that the above normalization is not performed in this transmittance spectrum.
  • compositions according to Comparative Examples 1 and 2 were obtained in the same manner as in Example 2 except that the addition amounts of the phenylphosphonic acid and phosphate ester compounds were changed as shown in Table 5.
  • Comparative Example as in Example 2 except that 4-bromophenylphosphonic acid was used instead of phenylphosphonic acid and the addition amounts of 4-bromophenylphosphonic acid and phosphate ester compound were adjusted as shown in Table 5.
  • a composition according to 3 was obtained.
  • the compositions according to Comparative Examples 1 to 3 had low transparency, and in the compositions according to Comparative Examples 1 to 3, the copper phosphonate fine particles were not dispersed, and the copper phosphonate fine particles were aggregated.
  • compositions according to Comparative Examples 1 to 3 are considerably difficult to use as a light-absorbing composition, and an optical filter could not be produced using the compositions according to Comparative Examples 1 to 3.
  • the light-absorbing agent formed by the phosphonic acid represented by the formula (a) and copper ions is included.
  • the ratio of the phosphonic acid content to the phosphate ester content is 0.10 to 0.48 on a mass basis
  • the ratio of the phosphonic acid content to the copper ion content is Is 0.45 to 0.80 on the basis of the amount of substance (mole), suggesting that the fine particles of the light absorber are easily dispersed well.
  • Comparative Example 4 was carried out in the same manner as in Example 2 except that n-butylphosphonic acid was used instead of phenylphosphonic acid and the addition amounts of n-butylphosphonic acid and phosphate ester compound were adjusted as shown in Table 5. Such a light-absorbing composition was obtained. Except that hexylphosphonic acid was used in place of phenylphosphonic acid, and the addition amounts of hexylphosphonic acid and phosphate ester compound were adjusted as shown in Table 5, light according to Comparative Examples 5 and 6 was prepared in the same manner as in Example 2. An absorbent composition was obtained.
  • Light absorption according to Comparative Example 7 was performed in the same manner as in Example 2 except that ethylphosphonic acid was used instead of phenylphosphonic acid, and the addition amounts of ethylphosphonic acid and phosphoric ester compound were adjusted as shown in Table 5. A composition was obtained.
  • the light absorbing compositions according to Comparative Examples 4 to 7 had high transparency, and the light absorbent fine particles were well dispersed in the light absorbing compositions according to Comparative Examples 4 to 7.
  • FIGS. 15 to 18 show transmittance spectra of the optical filters according to Comparative Examples 4 to 7, normalized according to the above conditions (1) and (2), respectively.
  • the solid line graphs show the transmittance spectrum normalized according to the condition (1)
  • the broken line graphs show the transmittance spectrum normalized according to the condition (2).
  • Table 6 shows main values related to the transmittance spectra of the optical filters according to Comparative Examples 4 to 7, normalized according to the above conditions (1) and (2).
  • the light of the optical filters according to Comparative Examples 4 to 7 is increased. It is conceivable to increase the content of the light absorber in the absorption layer. In this case, in the transmittance spectrum of the optical filter, there is a possibility that the UV cutoff wavelength is shifted to the long wavelength side while the IR cutoff wavelength is shifted to the short wavelength side, and the above conditions (IV) and (V) are satisfied. It seems to be advantageous to meet at the same time.
  • the range of design parameters allowed for simultaneously satisfying the above conditions (I) to (V) is wide.
  • the degree of freedom in designing an optical filter that satisfies the above conditions (I) to (V) is high.

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Optical Filters (AREA)
  • Laminated Bodies (AREA)
  • Glass Compositions (AREA)
  • Eyeglasses (AREA)
PCT/JP2018/041869 2018-05-07 2018-11-12 光学フィルタ及び光学フィルタの製造方法 WO2019215945A1 (ja)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2018-089164 2018-05-07
JP2018089164A JP6543746B1 (ja) 2018-05-07 2018-05-07 光学フィルタの製造方法

Publications (1)

Publication Number Publication Date
WO2019215945A1 true WO2019215945A1 (ja) 2019-11-14

Family

ID=67212271

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2018/041869 WO2019215945A1 (ja) 2018-05-07 2018-11-12 光学フィルタ及び光学フィルタの製造方法

Country Status (3)

Country Link
JP (1) JP6543746B1 (zh)
TW (1) TWI787402B (zh)
WO (1) WO2019215945A1 (zh)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116496682A (zh) * 2022-01-19 2023-07-28 白金科技股份有限公司 有机金属络合物涂布液和近红外线吸收膜
WO2023162864A1 (ja) * 2022-02-22 2023-08-31 日本板硝子株式会社 光学フィルタ、光吸収性組成物、光学フィルタを製造する方法、センシング装置、及びセンシング方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022080217A1 (ja) 2020-10-16 2022-04-21 日本板硝子株式会社 光学フィルタ、撮像装置、及び光学フィルタの製造方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004122701A (ja) * 2002-10-07 2004-04-22 Mitsubishi Plastics Ind Ltd ポリシロキサン薄膜転写用シート
JP2014168895A (ja) * 2013-03-04 2014-09-18 Daicel Corp 積層体及びその製造方法
JP2017072662A (ja) * 2015-10-05 2017-04-13 コニカミノルタ株式会社 光学フィルム、光学フィルムの製造方法、光学フィルム積層体の製造方法、および合わせガラスの製造方法
WO2017073756A1 (ja) * 2015-10-30 2017-05-04 大日本印刷株式会社 光学フィルム、偏光フィルム、偏光フィルムの製造方法、および画像表示装置
JP6267823B1 (ja) * 2017-07-27 2018-01-24 日本板硝子株式会社 光学フィルタ、カメラモジュール、及び情報端末
JP2018018094A (ja) * 2016-04-21 2018-02-01 日本板硝子株式会社 赤外線吸収性組成物、赤外線カットフィルタ、及び撮像光学系
JP6339755B1 (ja) * 2016-11-14 2018-06-06 日本板硝子株式会社 光吸収性組成物及び光学フィルタ

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004122701A (ja) * 2002-10-07 2004-04-22 Mitsubishi Plastics Ind Ltd ポリシロキサン薄膜転写用シート
JP2014168895A (ja) * 2013-03-04 2014-09-18 Daicel Corp 積層体及びその製造方法
JP2017072662A (ja) * 2015-10-05 2017-04-13 コニカミノルタ株式会社 光学フィルム、光学フィルムの製造方法、光学フィルム積層体の製造方法、および合わせガラスの製造方法
WO2017073756A1 (ja) * 2015-10-30 2017-05-04 大日本印刷株式会社 光学フィルム、偏光フィルム、偏光フィルムの製造方法、および画像表示装置
JP2018018094A (ja) * 2016-04-21 2018-02-01 日本板硝子株式会社 赤外線吸収性組成物、赤外線カットフィルタ、及び撮像光学系
JP6339755B1 (ja) * 2016-11-14 2018-06-06 日本板硝子株式会社 光吸収性組成物及び光学フィルタ
JP6267823B1 (ja) * 2017-07-27 2018-01-24 日本板硝子株式会社 光学フィルタ、カメラモジュール、及び情報端末

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116496682A (zh) * 2022-01-19 2023-07-28 白金科技股份有限公司 有机金属络合物涂布液和近红外线吸收膜
JP2023105786A (ja) * 2022-01-19 2023-07-31 白金科技股▲分▼有限公司 有機金属錯体コーティング液と近赤外線吸収フィルム
WO2023162864A1 (ja) * 2022-02-22 2023-08-31 日本板硝子株式会社 光学フィルタ、光吸収性組成物、光学フィルタを製造する方法、センシング装置、及びセンシング方法

Also Published As

Publication number Publication date
JP6543746B1 (ja) 2019-07-10
JP2019197082A (ja) 2019-11-14
TW201946978A (zh) 2019-12-16
TWI787402B (zh) 2022-12-21

Similar Documents

Publication Publication Date Title
JP6386687B1 (ja) 光吸収性組成物
JP6878637B2 (ja) 赤外線吸収層用組成物、赤外線カットフィルタ、及び撮像装置
JP6232161B1 (ja) 光学フィルタ
JP6864637B2 (ja) 赤外線カットフィルタ
JP6606622B2 (ja) 液状組成物及び吸収層
WO2019215945A1 (ja) 光学フィルタ及び光学フィルタの製造方法
JP2020064315A (ja) 光学フィルタ用組成物
JP2019159343A (ja) 光吸収性組成物及び光学フィルタ
JP2019197212A (ja) 光学フィルタ及び光学フィルタの製造方法
JP6368443B1 (ja) Ｕｖ‐ｉｒ吸収性組成物
JP6368444B1 (ja) 光学フィルタの製造方法
JP2019028433A (ja) 光学フィルタ
JP2019028420A (ja) 光学フィルタ
JP2020073983A (ja) 光学フィルタ、カメラモジュール、及び情報端末

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18917663

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18917663

Country of ref document: EP

Kind code of ref document: A1